Polymerizable triazines and polymers thereof



United States Patent Ofiice 3,053,799 Patented Sept. 11, 1962 Thisinvention relates to a new class of organic compounds and to the methodsfor their preparation. More particularly, the invention relates to novelepoxy-substituted triazine compounds and to their preparation andutilization. More specifically, it deals with reactive epoxytriazinederivatives suitable as monomers for the preparation of valuablepolymeric products, and as stabilizing agents, tanning agents,lubricants, chemical intermediates, and for other uses.

Specifically, the invention provides new and particularly useful organiccompounds which may be described as having a symmetrical triazinenucleus to which it is attached, as a substituent, at least onesubstituted epoxy group.

It is an object of this invention to provide a new class of s-triazinecompounds. It is also an object of this invention to provide novelepoxy-substituted triazine compounds and methods for their preparation.It is also a further object of this invention to provide novelepoxysubstituted triazines which are useful and valuable in industry,particularly as stabilizers for halogen-containing polymers, such as forvinyl chloride and its copolymers. It is an object of this invention toprovide new and useful chemical intermediates for the chemical industryas well as to provide a preparation for new compounds valuable asplasticizers, lubricants, and softening agents for other polymers andsynthetic resins. It is also an object of this invention to provideimproved polymerization products derived from said novel compoundscontaining epoxy groups.

It is a further object of this invention to provide new monomers fromepoxy-substituted triazines as Well as new polymers derived therefrom bypolymerizing a mass comprising these new monomers containing at leastone substituted epoxy (oxirane) group attached as a substituent to thetriazine ring.

It is an added object of this invention to provide new and usefulpolymers as well as copolymers by polymerizing a mass comprising morethan one new monomer of this invention, or at least one monomer of thisinvention with at least one other polymerizable compound, or with othertypes of epoxy-substituted compounds, such as the polyepoxy-reactionproducts of the bisphenols and epichlorohydrins.

Another object of this invention is to provide thermoplastic andthermosetting polymers.

These and other objects of this invention are accomplished by the novelcompounds of this invention comprising triazine derivatives to which areattached specific substituted epoxy groups.

The compounds of this invention are represented graphically by thefollowing general formula:

wherein n represents an integer having a value of at least one and notmore than three, Y is any monovalent radical, such as more fullyillustrated hereinafter, and B is a specific substituted epoxy radical,also more fully described hereinafter. In each of the compounds of thisinvention there is at least one substituted epoxy group B attached tothe triazine nucleus. Thus, when n is one, Y is two; when n is two, Y isone; and when n is three, no Y groups are attached to the triazine ring.

When the trivalent symmetrical triazine nucleus,

is represented by the symbol (C N the compound-s of this invention canbe represented as Y (C N )B, Y(C N )B and (C N )B or collectively as Theversatility of these new compounds is outstanding because of the largenumber of substituted triazines which can be prepared readily. Forexample, when the triazine rings of this invention contain only one Bgroup, the other two valencies of the triazine ring can be attached totwo other identical Y groups, for example to two methoxy groups, -OCH orto two amino groups, e.g. NH or to two substituted amino groups, e.g.N(CH or two different Y groups, for example an ethoxy group -OCH CH anda methoxy group --OCH or to an alkoxy group OR, and an aminoorsubstituted amino group NR etc. Further diversification can be obtainedin the variations possible in the substituted epoxy group itself, as forexample, the epoxy group can be part of a three carbon chain, e.g.

CH;OHCH2 or an eight carbon atom chain -OH2OH20H)CH2OHOHCH2OH3 whereinthe epoxy group is 5, 6 epoxy, or an isomer of the same chain whereinthe epoxy group is in a difierent location as in a 4, 5 epoxy position,e.g.,

-CH2CH3OHaOH-OHOH2CH2OH5 Still further diversification is obtainedthrough the epoxy substituent, as for example when more than one oxiraneor epoxy group is located in the structure of the substituent B as forexample, in the structure In other cases, where two B groups areattached to the triazine rings, these groups can be the same andcontain, for example, only one epoxy group, or they can be diiferentgroups containing only one epoxy group each, or they can be difierentwith one B group containing a single epoxy group and the other B groupcontaining more than one epoxy group. In still other cases, wherein thetriazine ring has three B groups attached to it, the B groups can be thesame or diiferent, thereby increasing the versatility of the newcompounds of this invention.

The compounds of this invention polymerize readily. When these new epoxycompounds contain only one epoxy group and no other polymerizable orcoreactive group, soluble, fusible polymers are obtained. When thecompounds of this invention contain two epoxy groups, insoluble,infusible polymers can be prepared therefrom whether the two epoxygroups are located in a single B substituent group, or in two Bsubstituent groups each containing an epoxy structure. Insoluble,infusible polymers are also obtained when the B substituent containsonly one epoxy group and at least one Y group is polymerizable or iscoreactive with the oxirane structure. Thus, in the compounds of thisinvention Y can be any polymerizable, or non-polymerizable monovalentradical attached to the triazine ring. For example, Y can be hydrogenand alkyl, aryl, aralkyl, alkaryl, cycloaliphatic and heterocyclicgroups and their chloro, fluoro, alkoxy, aryloxy, acyloxy derivatives,such as methyl, ethyl, propyl, isopropyl, butyl, octyl, decyl,chloroethyl, fluoropropyl, cyclohexyl, cyclopentyl, phenyl,chlorophenyl, fluorophenyl, xenyl, naphthyl, tolyl, isopropyl phenyl,benzyl, phenethyl, phenyl propyl, acetoxy benzyl, ethoxy propyl, methylnaphthyl, vinyl, allyl, methallyl, allyl phenyl, etc., radicals; Y canalso be hydroxyl and the alkoxy and aryloxy radicals derived fromaliphatic, cycloaliphatic, aromatic and heterocyclic hydroxy compounds,such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol,isobutyl alcohol, deeyl alcohol, phenol, the o-, m-, and p-cresols, thexylenols, naphthols, ethylene glycol, methyl glycol ether, butyl glycolether, glycerine, pentaerythritol, hydroxy naphthalene, hydroxypyridine, as Well as the alkoxy and aryloxy radicals of hydroxy acidsand esters such as lactic acids, ethyl lactate, salicyclic acid, methylsalicylate; and in addition Y can be an amino group, NH or the radicalof a monoor di-substituted amino group, for example, the radicalsderived from ethyl amine, methyl amine, butyl amine, nonyl amine,dimethyl amine, aniline, naphthyl amine, ethanol amine, diethanolamine,diisopropanol amine, methyl aniline, piperidine, amino pyridine,hydrazine, symmetrical dimethyl hydrazine, unsymmetrical dimethylhydrazine, as well as the radicals of the amino-acids, amino-amides,amino-nitriles, specific examples of which are:

NHGHzCOOCHa, N(CH2)5COOCH=CHn NHCHzCON(CHa)2, NHCHrON NHCaHicN, NHCIEhNHOCOHa the radicals of semicarbazides, such as semicarbazide itself,4-methyl semicarbazide, etc., as disclosed in my U.S. Patent No.2,295,565, issued September 15, 1942; the guanazo radical which isattached to the triazine ring by reacting dicyandiamide with a hydrazinetriazine as shown in my U.S. Patent No. 2,295,567, issued September 15,1942; the radicals of urea and substituted ureas, such as NHCONH CHNHCONH, etc., which may be attached to the triazine ring as shown in myU.S. Patent No. 2,312,688, issued March 2, 1943; radicals of aminoarylsulphonamides, e.g. NHC H SO NH NHC H SO- NHCH etc., as shown in my U.S.Patent No. 2,312,697, issued March 2, 1943; radicals of acyl hydrazineand substituted hydrazines, such as H3o-o70m Y can also be thepolymerizable radical of the acrylic,

methacrylic, chloracrylic ester or amide of amine alcohols or dialcoholsand diamines, e.g.,

CHFCH C O O GHzCHzO-. CH CHC O O CH2CH2NH- 0H3 Cl etc.,; the radicals ofpolymerizable aminated or hydroxylated alkylene aryl compounds, forexample,

4 etc.,; the radicals of malonic and substituted malonic esters,nitriles and amides, e.g.,

HC-(COOCHah, CH(CN):

CN etc.,; the

H --P(OR)2 radical such as 0 CH3 II etc., or a triazine ring, e.g., (CHNH) C N or through a bridge, such as (CH N (C N )NHCH CH NH-,

(HO) (C N )NHCH CH O, etc., or the group can represent the remainder ofthe molecule, to yield, for example, compounds of the structure as wellas those structures linked through carbon atoms, sulfur atoms, oxygenatoms, etc., as, for example,

( a 3) 2 2 3 a) 2 a 3) 2 2 3 3) (B) (Y) (C N )OCH CH O (C N B etc.

Y can also be such groups as OH, Cl, Br, F, CN, COOR, CONR as well asthe B group. When one of Y groups attached to the triazine ring containsa polymerizable ethylenic group, not inhibited by other groups or atomsin the monomer, polymers as well as copolymers can also be prepared withother monovinyl or monovinylidene monomers to produce modifiedthermoplastic compositions which can be converted to the insoluble,infusible state by further polymerization through the epoxy group andare useful in molding, laminating, casting, coating, and adhesiveapplications, and for other purposes. Insoluble, infusible polymers arealso obtained by copolymerization with polyvinyl compounds. Thesepolymers can be prepared by polymeriz ing a mass comprising thevinyl-substituted monomers of this invention, and can be modified bycopolymerization with at least one other polymerizable compoundcontaining the structures or groupings such as the unsaturated alkydresins, the acrylic and alkacrylic acids and their derivatives, such astheir esters, amides and corresponding nitriles, for example, acrylicacid, methyl acrylate, butyl acrylate, allyl acrylate, ethylene glycoldiacrylate, acrylonitrile, methacrylonitrile, methacrylic acid, methylmethacrylate, etc.; the itaconic acid monoesters and diesters, such asthe methyl, ethyl, phenethyl, allyl, dimethallyl, the maleic and fumaricacid monoesters, diesters and their amide and nitrile compounds, suchas, ethyl allyl maleate, fumaryl dinitrile, dimethallyl fumarate, etc;the ethers, such as vinyl phenyl ether, methallyl allyl ether, vinylallyl ether, vinyl meth allyl ether, allyl crotyl ether, vinyl crotylether, hydroquinone divinyl ether, propargyl allyl ether, divinyl methylglyceryl ether, etc.; the aryl ethylenes, such as, styrene, p-methylstyrene, the 0-, m-, and p-divinyl benzenes, vinyl naphthalene, diallylnaphthalene, dimethallyl carbazole, vinylpyridine, etc.; the polyolefinsand their polymerizable derivatives, such as, phenyl butadiene,chloroprene; low molecular weight polymers, such as, the dimers,trimers, tetramers, etc. of butadiene, isoprene, etc.; cyanuric acidderivatives, such as diallyl cyanurate, triallyl c'yanurate, tn'vinylcyanurate, or, in general, tn'azine compounds having at least onepolymerizable or copolymerizab le unsaturated group attached directly orindirectly to the triazine ring; as well as the partial, soluble, orfusible polymers of the hereinabove listed monomers, etc.

Additional examples of cornonomers are the vinyl esters, such as theacetate, propionate, stearate, fluoride, bromide, chloroacetate, etc.,vinyl ketones, methyl vinyl ketones etc. Polymerization can be effectedby freeradical generating catalysts, such as benzoyl peroxide, or byanionic or cationic catalysts.

When one of the Y groups attached to the triazine ring contains areactive NH or NH grouping, the compound can be condensed with aldehydesand ketones, such as formaldehyde, acetaldehyde, propionaldehyde,acrolein, glyoxal, acetone, ketone, diketone, etc., alone or in thepresence of other aldehyde-reactable compounds, such as urea, thiourea,methyl urea, hydroxyethyl urea, dicyanadiamide, quanidine, biguanidine,amino-triazales, triarninotriazine, tri(methylamino)triazine, ethylenediamino, phenylene, diamine, aminophenol, monoaminoguanazole,diaminoguanazole, diaminophenylguanazole, phenol, cresols, phenylphenol,p,p'-dihydroxydiphenylpropane, polyvinyl alcohol, polyacrylamide,polyethyleneirnine, etc. i

Particularly, however, this invention is concerned with triazinecompounds containing substituted epoxy groups in which E of the aboveformula represents the structure -AZX wherein A represents O-, S--, andNR, in which R represents hydrogen and a hydrocarbon radical, such asalkyl, aryl, alkaryl, aralkyl, etc. radicals; Z represents a divalentaromatic hydrocarbon radical, and X is an epoxy substituted alkylradical. Thus, the compounds of this invention have the formula:

CsNa 0 50 CO 0 C113 CH3 0 OOHCaHaCHCH-CH2 OCOCHa CaHn-CsNaSCwHaCHzCHaCH-CH:

O CaHa(O C 0 CH3) CHzOE7CHCmH (CH3) zN-CaNa In the triazine monomers ofthis invention, Z represents a divalent aromatic radical, predominantlyhydrocarbon, having an aryl nucleus between said valencies includingaralkylene and alkarylene, which groups can have substituents such aschloro, fluoro, alkoxy, aryloxy, acyloxy, etc. groups.

Illustrative examples of such divalent radicals include:

NHCsHs N(CHEC6HS)I etc.

The substituent groups such as the alkoxy, aryloxy, acyloxy, alkylamino, aryl amino, etc. radicals are advantageously radicals of no morethan about ten carbon atoms, such as methoxy, ethoxy, butoxy, pentoxy,octoxy, propionoxy, butyroxy, valeroxy, capryloxy, benzoxy,phenylacetoxy, toluoxy, etc. Other groups, such as nitroso, nitro, etc.,can also be used as substituent groups on the Z group, provided they areinert during the preparation and use of the monomer. Any portion of theZ group which is aliphatic can be saturated or unsaturated, e.g.,

etc. Also, without departing from the spirit of this invention, thecarbon atoms in the divalent radical Z, can be interrupted by an atomother than carbon, e.g.

etc.

While other hydrocarbon and substituted hydrocarbon groups are alsoetfective as Z groups, the groups indicated above are preferred forreasons of availability and economy.

9 A few illustrative examples of the structures of the epoxy alkylgroup, X, are:

-OH CH-OH CHzCHz-CHOH2 OCHa 0 The epoxy-substituted alkyl groups, X,attached to the triazine nucleus comprise those alkyl groups having a1,2-epoxy group; that is, a

structure, in the alkyl group, containing from 2 to 20 carbon atoms inthe alkyl group which can be saturated, unsaturated, branched, orunbranched and open-chain as indicated in the structures hereinabove.Particularly preferred alkyl radicals are the monoepoxy-substitutedalkyl groups containing from 2 to 8 carbon atoms and having an epoxy inthe terminal position. Typical examples of the epoxy alkyl groupsinclude the folowing:

propanyl-2) cycloaliphatic and heterocyclic groups and their chloro,fluoro,

alkoxy, aryloxy, acyloxy derivatives, such as methyl, ethyl, propyl,isopropyl, butyl, octyl, decyl, chloroethyl, fluoropropyl, cyclohexyl,cyclopentyl, phenyl, chlorophenyl, fluorophenyl, xenyl, naphthyl, tolyl,isopropyl phenyl, benzyl, phenethyl, phenyl, propyl, 'acetoxy benzyl,ethoxy propyl, methyl naphthyl, vinyl allyl, methallyl, allyl phenyl,etc. radicals.

SYNTHESIS The novel compounds of this invention can be prepared by anumber of methods. For example, they can be pre pared by epoxidizingunsaturated triazine derivatives, as for example by epoxidizingmonomethoxy-4,6-diallyloxy- S-triazine. The epoxidation of theunsaturated compounds is performed advantageously by reacting theunsaturated compound with an epoxidizing agent at a temperature betweenabout -20 C. to 50 C., preferably under anhydrous conditions. Effectiveepoxidizing agents for this type of reaction are organic peracids, suchas peracetic acid, perbenzoic =acid, monoperphthalic acid, as well asacetaldehyde monoperacetate, and the like. The peroxidation ispreferably carried out'in a suitable mutual solvent for the products ofthe reactants. A number of solvents can be used, such as chloroform,ethyl, ether, dichloromethane, benzene, ethyl acetate, and the like, andthe choice of the solvent depends on the product being synthesized.

The synthesis of the compounds of this invention can be illustrated asfollows:

ON 00 011-011 omooorr 3 A o The equation can be generalized as follows:

peroxidation an( s a) u sn( aNa) n wherein X is an alkenyl radicalcorresponding to the epoxidized alkyl radical, and Z and A have the samemeaning as hereinbefore described.

The novel compounds of this invention can also be prepared by reactingthe corresponding cyanuric halide with the appropriate substituted epoxyintermediate, e.g.,

hydrohalide acceptor This equation can be generalized as follows:

hydrohalide conveniently be employed in stoichiometn'c quantitiesalthough in some cases a slight or a large excess of the less costlyreagent may be used to insure higher conversions. In the reaction of thehalotriazine and the epoxy-intermediate, the hydrohalide acceptorpreferably should be one that will not react with either thehalotriazine or the epoxy group or cause polymerization of theepoxy-substituted triazine if monomeric materials are desired.

In introducing groups, other than the epoxy groups, into the triazinering, such as a non-reactive methoxy group by reaction of thehalotriazine and methyl alcohol,

reactive hydrohalide acceptors, such as sodium hydroxide, potassiumhydroxide, lithium hydroxide, calcium hydroxide, and their bicarbonatesand carbonates can be used. in the preparation of the epoxy-Substitutedtriazine, if monomeric materials are desired, the hydrohalide acceptorspreferably are weak inorganic bases and tertiary amines, such astriethyl amine, tributyl amine, pyridine, and the like. Upon completionof the reaction the product can be removed by filtration if it is asolid, or by decantation if it is an oil. Salts formed by the reactionbetween the hydrohalide and the acceptor can be removed by filtration orequivalent means, by having the reaction carried out in a medium, suchas a hydrocarbon, in which the salt is insoluble. Also, after isolation,the water insoluble epoxy-substituted triazine can be washed with waterto remove salt impurities.

In the practice of this invention it is not necessary to isolate themonomeric product, but the polymeric product can be prepared, in manycases, directly if desired. For example, the reaction between adihalotriazine or a tri halotriazine and an epoxy-intermediate can becarried out in the presence of a strong alkali, with a Slight excess ofthat required stoichiometrically, whereby the epoxysubstituted triazineis formed, and under the reaction conditions, a polymer product formedby polymerization of the oxirane groups is obtained. In other cases,polymerization can occur between an epoxy group as it is substituted onthe ring and another reactive group, such as an NH group already on thering.

In other cases the monomeric epoxy-substituted triazine can be isolatedas such and later polymerized and copolymerized. The halotriazines usedin the practice of this invention can be any of the halotriazines butare preferably the bromoand chloro-triazines. For economic reasons, thechlorotriazines are preferred.

The novel compounds of this invention are either substantially colorlessliquids, or solid or semi-solids and are soluble in a Wide variety ofsolvents, depending on the substituents, attached to the triazine ring.They are soluble in many oils and solvents and show compatibility withmany polymers, such as vinyl chloride polymers and copolymers, as wellas with polymerized oxirane compounds. They also act as stabilizingagents for chlorine and halogen containing polymers.

The products of this invention are especially useful in the preparationof commercially valuable polymerization products. They can bepolymerized by themselves or with other epoxy-monomers or polymers. Thehomopolymers of the mono-epoxy-substituted triazines of this invention,when they contain no other reactive group on the ring, can bepolymerized to substituted linear polyethers by catalysts such as zincchloride, sodium hydroxide, tertiary amines, etc. About 1-5 percent ofthe catalyst is usually sufiicient to produce polymers using atemperature in the range of l00 C.

Epoxy-substituted triazines containing at least two oxirane groups, orone oxirane group and another reactive group attached to the ring, aremore readily polymerized, and in most cases produce thermosettingpolymers. In some cases where another reactive group is attached to thetriazine ring together with at least one epoxy group, heat alone issuflicient to produce polymers. In those monomers that contain eithertwo epoxide groups and no other reactive group, or three epoxide groups,polymcrization products can be obtained by treating with a large varietyof catalysts, such as aluminum chloride, boron trifluoride; aminecatalysts, such as ethyleneamine, diethyleneamine, pyridine, pipen'dine,the phenylene diamines, aminealdehyde condensation products, and theamide-aldehyde condensation products, such as the condensation offormaldehyde with amines and amides, such as aniline, aminophenols,urea, thiourea, semi-carbazide, amino-triazines, and amino-diazines,hydroxyureas, etc.; the polyisocyanates, such as phthalic, terephthalic,oxalic, succinic, and the like. The amount of catalyst used will dependon the nature and activity of the catalyst, the specificepoxy-substituted triazine and the temperature conditions used, but inmost cases the amount of catalyst will vary from 0.1 percent to about 5percent by weight of the epoxy compound. A wide range of temperature canbe used in polymerizing the epoxy substituted triazines of thisinvention, for example, from l0 C. to about 150 C. or higher, and morepreferably between 20 C. and 120 C.

The epoxy-substituted triazine of this invention can be polymerizedalone or copolymerized with other polymerizable materials. Two or moredifierent epoxy-substituted triazines can be copolymerized together.Also, one or more epoxy-substituted triazines can be copolymerized withother kinds of epoxy containing compounds, such as ethylene oxide,propylene oxide, epichlorohydrin, glycidol, butadiene monoxide,butadiene dioxide; epoxyethers, such as the diglycidyl ethers ofdihydric phenols, such as resorcinol, catechol,p,p-dihydroxy-diphenyl-propane 2; p,p -dihydroxy diphenyl methane;polyepoxy-polyethers, such as are obtained by reacting under alkaline oracid conditions a polyhydric alcohol, such as ethylene glycols,glycerol, pentaerythritol and a halogencontaining epoxide, such asepichlorohydrin; monoand di-esters of epoxy-alcohols, such as2,3-epoxy-propylacctate, di(2,3-epoxy-propyl) phthalate, glycidylacrylate, glycidyl crotonate, and similar compounds.

The soluble, fusible polymers prepared from the epoxysubstitutedtriazines of this invention can be used in the preparation of coatingcompositions, impregnating compositions, viscosity improvers forlubricating oils and greases, as textile sizings, plasticizers and moldlubricants for other polymers, in the manner in which such compositionsare generally used, and for other uses.

The thermosetting homopolyrners and copolymers of this invention areinsoluble, infusible materials, and are useful as adhesives, castings,and potting compounds, for the preparation of laminated products andmolded compounds. The partially polymerized products of theseepoxy-substituted triazine containing a plurality of epoxy groups can beconverted to other derivatives by reaction with fatty acids andespecially drying oil fatty acids, such as oleic, lineoleic, linolenic'acid, etc., for the preparation of drying oil composition. Theepoxy-substituted triazines can also be used as chemical intermediatesby reaction with other compopnds, for example, with acetic acid and/oracetic anhydride to produce the diacetate corresponding to the dialcoholof the oxirane linkage. In general, these epoxy-substituted triazinescan be reacted with water to produce the corresponding glycols, or withorganic compounds containnig one or more active hydrogens, such as thealcohols, the acids, the amines, the phenols, etc., e.g. ethyl alcohol,succinic acid, aniline, phenol, and the like by reacting in the presenceof an acid or alkaline catalyst. These reactive hydrogen compounds canalso be polymeric, such as cellulose, polyvinyl alcohol,phenol-formaldehyde resins, the polyethylene amines, caprolactampolymers, polyamides, saturated and unsaturated polyesters, alkydresins, such as glyceryl phthalate, and oil-modified glyceryl phthalatesand the like.

The invention will be more fully described by the following examples.-This invention is not to be regarded, however, as restricted in any wayby these examples and they are used merely as means of illustration andnot by way of limitation. In these examples, as well as throughout thespecification, parts and percentages" shall mean parts by weight andpercentages by weight unless specifically provided otherwise.

"PREPARATION OF THE MONOMERS Synthesis A The preparation of the monomersof this invention is illustrated specifically by the synthesis of C N(OC H CH;-CH-CH1);

To a mixture of 18.4 parts of cyanuric chloride, 56 parts of tributylamine and parts of water cooled to 2-5 C., in a flask equipped withmeans for heating and stirring, is added slowly and with stirring 45parts of 13 para-(2,3-epoxypropyD-phenol. Upon completion of theaddition, the reaction is allowed to proceed for one hour at roomtemperature, after which the mixture is refluxed for 1 to 2 hours andthen allowed to cool to room temperature. The product is washed withwater to remove byproduct amine hydrochloride and dried under reducedpressure. Ultimate analyses for carbon, hydrogen, nitrogen, andmolecular weight give values of 68.4%, 5.21%, 7.96%, and 526.4, all ofwhich are in close agreement with the theoretical values. By differencethe oxygen content is 18.43%, which agrees closely with theoretical.

The theoretical content of the oxirane oxygen is 9.15% and the actualvalue will depend on the degree of conversion of the monomer to polymervarying from the theoretical value to lower values approaching zero; forexample, the theoretical value may be lowered by continued reflux duringthe condensation of the halotriazine derivative with the epoxy compound,or by the use of higher quantities of hydrohalide acceptor, or by theuse of other hydrohalide acceptors, such as sodium hydroxide, or simplyby heating the isolated intermediate or resin alone or with alkalis,acids, or salts, or with other coreactive ingredients.

When, instead of the (2,3-epoxypropyl)-phenol, another epoxy compound isused corresponding to the formula HAZX as previously definedhereinabove, then the corresponding triazine derivative is obtained, asfor example, when HSCsHrUHzCH-CI-Ig is used in equivalent amount,instead of the (2,3-epoxypropyl)-phenol, then (C3N3) (S CoH-1CH2CHCH2)3is obtained.

Synthesis B This method illustrates the peroxidation method of preparingthe new compounds of this invention.

To 47.7 parts of 2,4,6-tris(p-allylphenoxy)-1,3,5-triazinc in 150 partsof hexane is added 55 parts of 45% peracetic acid prepared according tothe procedure of Industrial and Engineering Chemistry, 39, 847 (1947).The reaction mixture is allowed to stand at room temperature for 24hours and then at 40 -50 C. for 3 hours. Thereafter, it is washed withtwo 100-part portions of water, dilute sodium carbonate solution, andagain with Water. The hexane is removed at reduced pressure and there isisolated the epoxy derivative corresponding to that prepared inSynthesis A.

Instead of the specific peroxidation method illustrated in this example,which is known as the preformed peracid method, other peroxidationtechniques can he used which are well known in the art, such as thein-situ method using formic or acetic acid and hydrogen peroxide withsulfuric acid, alkane sulfonic acids, or ion-exchange resins containingsulfonic groups, the acetaldehyde monoperacetate method, the tungsticacid-hydrogen peroxide method, etc.

As indicated in the previous synthesis, the substitution of othertriazine derivatives for C3N3 3 of this example will produce thecorresponding compound, for example, (CH NC N (OC H CH='CH will produceor in general, compounds of the formula Y 3 3 (D-ZX')n will yieldproducts of the formula 14 as previously described hereinabove, whereinX' is an alkenyl group corresponding to the epoxy-containing group X.

While there is a great variety in the types of monomers covered by thisapplication, it will be simple enough for any chemist to select which ofthe above types of preparation is best suited for preparation of aparticular monomer. Once a monomer of this invention has been selected,it is well within the skill of any chemist to determine whatintermediates would be best suited for its preparation according to theabove procedures, how to prepare them, if not easily available, and howto combine them according to well known standard chemical reactions. Forexample, when the groups to be added to a triazine nucleus aredifferent, it would be obvious for a chemist to react a cyanuricchloride first with the stoichiometric amount of one intermediate thatwould attach the first group, then with the stoichiometric amount of asecond intermediate that would react to attach the second group, andthen with the stoichiometric amount, or slight excess of a thirdintermediate to supply the third group, each reaction being promoted bythe well-known conditions for effecting each type of condensation.Depending on the availability or ease of preparation of theintermediates, it is generally advantageous to assemble chemical groupsin an intermediate in such a manner that one condensation reaction willefiect the attachment for each respective side group to the triazinenucleus. However, the desirability of step-wise attachment is within theskill of any chemist to determine.

By the procedures indicated above, the following compounds are preparedfor use hereinafter in the following examples.

EXAMPLE I This example illustrates the conversion of the monomers ofthis invention to polymers with alkaline or acid substances or withactive salts. Ten parts each of monomers A to H inclusive are mixedrespectively with one to two parts of sodium hydroxide, calciumhydroxide, po tassium hydroxide, aluminum chloride, boron fluorideetherate, phthalic anhydride, and succinic acid, respectively. Thetemperature is varied in each case, using 20 C. for A; 40 C. for B; 60C. for C; C. for D; C. for E; C. for F; C. for G; and C. for H.

EXAMPLE II Ten parts of monomer A are added to 50 parts of dioxanecontaining 0.1 part NaOH and the mixture heated at 60 C. to polymerizethe monomer and give an increased viscosity. Continued heating resultsin a cross-linked gel.

*If desired, the heating can be discontinued before gellation to give apartial polymer. Gellation can be retarded considerably by using amixture of monomers, for example by using a mixture of monomers H and D.Instead of monomer D, other oxirane compounds, such as styrene oxide, orepoxidized methyl oleate can be used.

EXALELE III Instead of polymerizing a single triazine monomer, a mixtureof equal parts of monomers A and B are mixed together and five parts ofp,p-diaminodiphenyl sulfone are added to each 100 parts of the mixtureand the mixture molded at 100 C. to produce a product which is lessbrittle than when monomer A is used alone. A more flexible product isproduced when monomer B in the above formulations is replaced by monomerD which has only one exirane linkage.

EXAMPLE IV Example III is repeated using monomer A and the diepoxycompound instead of monomer B, and a copolymer is obtained comparingfavorably with the properties of the copolymers of Example III.

EXAMPLE V One mole of monomer A is heated with 3 moles of aceticanhydride to produce a composition comprising substantially thehexa-acetate of the monomer due to the opening of the oxirane rings,represented as (01120 O) 20 CC Reaction with alcohols, amides, amines,mercaptans, ammonia, hydrogen, cyanide, phenols, antimony trichloride,arsenic trichloride, ethyleneimine, etc., achieves similar opening ofthe oxirane rings.

EXAMPLE vr Twenty-five parts of monomer G are dissolved in a mixture of50 parts of acetone and 50 parts of dioxane containing 0.25 part ofbenzoyl peroxide and the mixture refluxed for 24 hours to produce apolymer containing polymerizable oxirane groups. One part ofdicyandiamide is added to the solution. Films are case, the solventevaporated at 7080 C. and the film cured at 125 C. for one-half hour toyield a product insoluble in benzene, chloroform, acetone, dioxane, andother active organic solvents.

Instead of producing a homopolymer, a copolymer can be prepared by usingat least one other monomer containing a CH =C a CH =CH, or a linkage,such as styrene, vinyl acetate, ethyl methacrylate, maleic anhydride,acrylonitrile, etc., for example:

A mixture of 20 parts of styrene, parts of monomer G, 0.25 part ofbenzoyl peroxide in 100 parts of acetone, is polymerized by reflux for24 hours, then allowed to cool and methanol added to precipitate thepolymer which is dried under reduced pressure. Ten parts of the polymerare mixed with one part of phthalic acid and the mixture molded at 2,000pounds per square inch at 130 C. to produce a water-resistant,solvent-resistant, and heatresistant composition. Dicyandiamide, orp,p-diaminodiphenyl sulfone is used in place of the phthalic acid togive similar results.

EXAMPLE VII A 30 percent solution is prepared from monomer H in asolvent mixture of equal parts of dioxane and acetone, to which is addedtwo parts of 4,4'-diamino-diphenyl sulfone. Paper sheets are impregnatedWith the resin solution and dried at 75 -90 C. to remove solvent be- 16tween impregnations until a content of 65 percent resin is obtained inthe sheet. Multiple 5 x 5 inch sheets are superimposed and the assemblypressed between stainless steel platens in a press at a temperature ofabout C. at 5,000 pounds per square inch for 30 minutes. The laminatedsheet has a hard, abrasive-resistant surface and excellent boiling waterresistance, which is lower than a comparable laminate produced withtriglycidyl cyanurate.

EXAMPLE VIII Forty parts of acrylic acid, 400 parts of butyl acrylate,1,000 parts styrene, 1,500 parts amyl acetate, and 25 parts of cumenehydroperoxide are refluxed for 5 to 7 hours. To this solution there isadded 500 parts of monomer A. A film is cast from the mixture and bakedat 325 F. for 30 minutes. The cured film has greater mar resistance thana comparable film prepared with triglycidyl cyanurate.

Excellent results are also obtained when monomers B, C, E, F, G, and H,respectively, are used instead of monomer A.

EXAMPLE IX This example illustrates the preparation of foams using thenew compounds and polymers of this invention. 70 parts of monomer B, 15parts of polyethylene polyimine, 0.75 part of diazo aminobenzene, 0.1part of hexane are mixed together and heated at 200-230 F. to produce afoam having approximately ten times the original volume of unfoamedmaterial and a compressive strength of over 150 pounds per square inch.Similarly, foams are prepared by the use of monomers A, C, E, F, G, andH, respectively.

EXAMPLE X Fifty parts of monomer A, 300 parts of soyabean fatty acidsare esterified in 5 hours at l00-225 C. with continuous removal of waterusing xylene as an azeotroping agent. As a drier there is added 0.05percent cobalt naphthenate. A film cast on glass test panel is allowedto air dry for five days and then tested in a weatherometer. At the endof seven days exposure, the film is essentially colorless, in contrastto intense yellowing of another film prepared from the reaction productof the soyabean fatty acids and the epichlorohydrin derivative ofbis-phenol.

Similar results are obtained when monomers B, C, E, F, G, and H,respectively, are used instead of monomer A.

EXAMPLE XI Sixty parts of polyvinyl chloride and 40 parts of dioctylphthalate are mixed in a rolling mill to a homogeneous blend. During theprocessing some fuming occurs and some discoloration becomes apparent.When a molded sheet is heated at 325 F. for 30 minutes, the clarity ofthe sheet becomes poorer and discoloration becomes noticeable. When tenparts of the dioctyl phthalate are replaced in the formula by monomer H,no discoloration or fuming is noticed during the milling and when amolded film is tested at 325 F. for 30 minutes, the clarity and color ofthe molded product remains substantially unchanged.

Copolymers of vinyl chloride 50-50 with vinyl acetate, and 50-50 methylmethacrylate, respectively, are used in place of polyvinyl chloride withsimilar results.

Similar results are also obtained when monomers A, B, C, D, and G,respectively, are used instead of monomer H.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details shown above, except insofar as they are defined inthe following claims.

The invention claimed is:

1. A composition of matter consisting essentially of spasm wherein n isan integer having a value of at least 1 and not more than 3; A is adivalent radical selected firom the class consisting of --O-, S, and NR;R is selected from the class consisting of hydrogen and hydrocarbonradicals containing no more than about 14 carbon atoms therein; Z is adivalent aromatic hydrocarbon radical containing no more than about 20carbon atoms therein; X represents an oxirane-alkyl radical containingno more than about 20 carbon atoms therein; and Y represents amonovalent radical.

2. A composition of claim 1, in which said monomer is C3N3 O CaH4C 2 2)a3. A composition of claim 1, in which said monomer isCH30C3N3(OOBH4CH2CECH)7 4. A composition of claim 1, in which saidmonomer is [(CHz)zN]-C3Nz(0CaH GHzCHCH2)2 5 A composition of claim 1, inwhich said monomer is [(OHS) 2Nl2C3N3-O CuH; CH-CH3 0 6. A compositionof claim 1, in which said monomer isOHFCHOONHGHflOH2O-C3N3(OC6H4CE-7OH2M 7. A composition of claim 1, inwhich said monomer is Ho'-OaN3(SOaH CH2CHzCH-GHz)2 8. A composition ofclaim 1, in which said monomer is OH=CHCH4OOQN3(OCH4CH-OHCHQ)Q 9. Acomposition of claim 1, in which said monomer is (CH OMORNTOC H4CH2CH-CH(CHi)nCH-CH2 3 10. A composition of claim 9, in which said polymerizablemass also comprises an unsaturated alkyd resin having aliphaticunsaturation therein.

11. A composition of claim 1, in which said polymerization product is apolymerization product in which said polymerizable mass comprises atleast one other copolymerizable monomer.

12. A copolyrnerization product of claim 11, in which said othercopolymerizable monomer is an unsaturated alkyd resin having aliphaticunsaturation therein.

13. A composition of claim 11, in which said copolymerizable monomer isa vinyl monomer.

14. A composition of claim 13, in which said vinyl monomer is styrene.

15. A composition of claim 13, in which said vinyl monomer isacrylonitrile.

16. A composition of claim 11, in which said copolymerizable monomer isethyl methacrylate.

17. A composition of claim 11, in which said polymerizable masscomprises an unsaturated alkyd resin having aliphatic unsaturationtherein and another copolymerizable monomer.

18. A composition of claim 17, in which said copolymerizable monomer isstyrene.

19. A compound having the formula I N N (Y) 3-H I (-A- Z ""X) n whereinn is an integer having a value of at least 1 and not more than 3; A is adivalent radical selected from the class consisting of O-, --S-, and NR;R is selected from the class consisting of hydrogen and hydrocarbonradicals containing no more than about 14 carbon atoms therein; Z is adivalent aromatic hydrocarbon radical containing no more than about 20carbon atoms therein; X represents an oxirane-alkyl radical containingno more than about 20 carbon atoms therein; and Y represents amonovalent radical.

20. A compound having the formula CaN3(O CaH4CHaCH-CHz);

21. A compound having the formula CHaO-CSN3(OCaH CHnCE7OH2M 22. Acompound having the formula (CHs)2 a a(Q a 4 H2CE/OH2)2 23. A compoundhaving the formula S)I ]E BNBOCaH4CH-CH 24. A compound having theformula CHFOHCONHOH CHzW-OaNAOO H C1EE7OHM References Cited in the fileof this patent UNITED STATES PATENTS 2,810,706 Frazier et al Oct. 22,1957 2,917,493 Phillips et al Dec. 15, 1959 FOREIGN PATENTS 773,874Great Britain May 1, 1957

1. A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF A POLYMERIZATIONPRODUCT OF A POLYMERIZABLE MASS COMPRISING AT LEAST ONE MONOMER OF THESTRUCTURE
 11. A COMPOSITON OF CLAIM 1, IN WHICH SAID POLYMERIZATIONPRODUCT IS A POLYMERIZATION PRODUCT IN WHICH SAID POLYMERIZABLE MASSCOMPRISES AT LEAST ONE OTHER COPOLYMERIZABLE MONOMER.
 12. ACOPOLYMERIZATION PRODUCT OF CLAIM 11, IN WHICH SAID OTHERCOPOLYMERIZABLE MONOMER IS AN UNSATURATED ALKYL RESIN HAVING ALIPHATICUNSATURATION THEREIN.